EP4036160A2 - Film de polyester mat et son procédé de fabrication - Google Patents

Film de polyester mat et son procédé de fabrication Download PDF

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Publication number
EP4036160A2
EP4036160A2 EP21193708.1A EP21193708A EP4036160A2 EP 4036160 A2 EP4036160 A2 EP 4036160A2 EP 21193708 A EP21193708 A EP 21193708A EP 4036160 A2 EP4036160 A2 EP 4036160A2
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EP
European Patent Office
Prior art keywords
matte
polyester film
polyester
intrinsic viscosity
chips
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21193708.1A
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German (de)
English (en)
Other versions
EP4036160A3 (fr
Inventor
Wen-Cheng Yang
Te-Chao Liao
Chun-Cheng Yang
Chia-Yen Hsiao
Hao-sheng CHEN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nan Ya Plastics Corp
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Nan Ya Plastics Corp
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Filing date
Publication date
Application filed by Nan Ya Plastics Corp filed Critical Nan Ya Plastics Corp
Publication of EP4036160A2 publication Critical patent/EP4036160A2/fr
Publication of EP4036160A3 publication Critical patent/EP4036160A3/fr
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/04—Disintegrating plastics, e.g. by milling
    • B29B17/0412—Disintegrating plastics, e.g. by milling to large particles, e.g. beads, granules, flakes, slices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/04—Disintegrating plastics, e.g. by milling
    • B29B2017/042—Mixing disintegrated particles or powders with other materials, e.g. with virgin materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0094—Condition, form or state of moulded material or of the material to be shaped having particular viscosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/26—Scrap or recycled material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/0024—Matt surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0046—Elastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0072—Roughness, e.g. anti-slip
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
    • C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the disclosure relates to a matte polyester film and a method for manufacturing the same, in particular to a matte polyester film prepared by using both a physically regenerated polyester resin and a chemically regenerated polyester resin and a method for manufacturing the same.
  • the most common recycling method for waste PET bottles is the physical recycling method (or mechanical recycling method).
  • the physical recycling method is mainly to pulverize the waste PET bottle materials by a physical mechanical means; then placing the pulverized PET bottle materials in a high-temperature environment for melting; then pelletizing the molten PET bottle materials to form physically regenerated polyester chips.
  • the physically regenerated polyester chips may be used in subsequent processing operations.
  • the physically regenerated polyester chips produced by the physical recycling method usually have higher intrinsic viscosity (IV).
  • IV intrinsic viscosity
  • the solid-state polymerization method may only be used to increase the intrinsic viscosity of the physically regenerated polyester chips, and may not be used to reduce the intrinsic viscosity of the physically regenerated polyester chips.
  • the general film-making process usually has certain limitations on the intrinsic viscosity range of polyester chips.
  • the physically regenerated polyester chips produced by the physical recycling method are generally only suitable for bottle blowing and spinning processes, and not suitable for film extrusion.
  • the physically regenerated polyester chips suitable for a film-making process is mainly mixed the physically regenerated polyester chips and additional virgin polyester chips to reduce the overall intrinsic viscosity of the polyester materials.
  • this method may be not able to effectively increase the proportion of recycled polyester materials in the matte polyester film, and therefore the final matte polyester film product may not meet the demands of environmental protection. In other words, there may be a certain limit in the proportion of recycled polyester in the current matte polyester film that needs to be overcome.
  • the disclosure is to provide a matte polyester film and a method for manufacturing the same to overcome the shortcomings of the technology.
  • the disclosure is to provide a method for manufacturing a matte polyester film.
  • the method for manufacturing a matte polyester film includes the following steps: providing a recycled polyester material; physically regenerating a part of the recycled polyester material to form physically regenerated polyester chips; wherein the physically regenerated polyester chips have a first intrinsic viscosity; chemically regenerating another part of the recycled polyester material to form chemically regenerated polyester chips; wherein the chemically regenerated polyester chips have a second intrinsic viscosity less than the first intrinsic viscosity; mixing matte regenerated polyester chips, the physically regenerated polyester chips, and the chemically regenerated polyester chips according to a predetermined intrinsic viscosity so as to form a polyester masterbatch material; and melting and then extruding the polyester masterbatch material to obtain the matte polyester film having the predetermined intrinsic viscosity; the predetermined intrinsic viscosity of the matte polyester film is between 0.40 dL/g and 0.75 dL/g; the matte polyester film has an acid value between 10 mgKOH/g
  • the disclosure is to provide a matte polyester film.
  • the matte polyester film is formed by mixing, melting, and extruding a physically regenerated polyester resin and a chemically regenerated polyester resin according to a predetermined intrinsic viscosity, so that the matte polyester film has the predetermined intrinsic viscosity.
  • the predetermined intrinsic viscosity of the matte polyester film is between 0.40 dL/g and 0.75 dL/g; the matte polyester film has an acid value between 10 mgKOH/g and 80 mgKOH/g; the matte polyester film has a surface roughness (Ra) between 100 nm and 400 nm; and the matte polyester film has a friction coefficient between 0.2 and 0.6.
  • a content of isophthalic acid in the matte polyester film is between 0.7 mol% and 4.0 mol%; and a storage modulus of the matte polyester film measured at 150 ⁇ 2 °C and 10 Hz is between 4.2 ⁇ 10 9 dyne/cm 2 and 6.8 ⁇ 10 9 dyne/cm 2 .
  • the matte polyester film has a haze between 15% and 95%, and the matte polyester film has a visible light transmittance not less than 60%.
  • a content of biomass-derived ethylene glycol in the matte polyester film is not more than 5 wt%.
  • the matte polyester film has a predetermined intrinsic viscosity between 0.40 dL/g and 0.75 dL/g; the matte polyester film has an acid value between 10 mgKOH/g and 80 mgKOH/g; the matte polyester film has a surface roughness (Ra) between 100 nm and 400 nm; and the matte polyester film has a friction coefficient between 0.2 and 0.6.
  • a content of isophthalic acid in the matte polyester film is between 0.7 mol% and 4.0 mol%; and a storage modulus of the matte polyester film measured at 150 ⁇ 2 °C and 10 Hz is between 4.2 ⁇ 10 9 dyne/cm 2 and 6.8 ⁇ 10 9 dyne/cm 2 .
  • the matte polyester film has a haze between 15% and 95%, and the matte polyester film has a visible light transmittance not less than 60%.
  • a content of biomass-derived ethylene glycol in the matte polyester film is not more than 5 wt%.
  • the polyester masterbatch material may be adjusted to have a predetermined intrinsic viscosity, so as to be suitable for a film extrusion process, and a higher proportion of the recycled polyester masterbatch material is achieved.
  • One of the objects of the disclosure is to increase the proportion of recycled polyester materials in the matte polyester film, so that the matte polyester film product may meet the demands of environmental protection.
  • a method for manufacturing a matte polyester film is provided to effectively increase the proportion of recycled polyester material in the matte polyester film, and to provide the resulting matte polyester film with good processability.
  • the method for manufacturing the matte polyester film includes step S110 to step S150. It must be noted that the sequence of the steps and the actual operation method described in the present embodiment may be adjusted as needed, and are not limited to those described in the present embodiment.
  • Step S110 includes: providing a recycled polyester material.
  • the recycling method of polyester materials includes: collecting various types of waste polyester materials; classifying according to the types, colors, and uses of the waste polyester materials. Then, the waste polyester materials are compressed and packaged. Then, the packaged waste polyester materials are transported to a waste treatment plant.
  • the waste polyester materials are recycled PET bottles (r-PET), but the disclosure is not limited thereto.
  • the recycling method of polyester materials further includes: removing other objects (such as bottle caps, labels, and adhesives) on the waste polyester materials. Then, the waste polyester materials are pulverized by a physical mechanical means. Then, the bottle mouth, liner, and bottle body of different materials are separated by flotation. Then, the pulverized waste polyester materials are dried to obtain processed recycled polyester materials, such as recycled PET bottles (r-PET) bottle flakes, to facilitate the subsequent thin-film manufacturing process.
  • r-PET recycled PET bottles
  • the recycled polyester materials may also be, for example, directly purchased processed recycled polyester materials.
  • polyester refers to any type of polyester, especially aromatic polyester, and here in particular refers to the polyester derived from the copolymerization of terephthalic acid and ethylene glycol, namely polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • the polyester may also be, for example, polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), or polyethylene naphthalate (PEN).
  • the polyester is preferably polyethylene terephthalate and polytrimethylene terephthalate.
  • copolymers may also be used, particularly copolymers obtainable by using two or more dicarboxylic acids and/or two or more diol components.
  • the r-PET bottle flakes contain isophthalic acid (IPA) as a diacid unit. Therefore, the final matte polyester film also contains isophthalic acid. In particular, based on a total weight of 100 mol% of the matte polyester film, the content of isophthalic acid in the matte polyester film is between 0.5 mol% and 5 mol%.
  • IPA isophthalic acid
  • the r-PET bottle flakes contain biomass-derived ethylene glycol as the diol unit. Therefore, the final matte polyester film also contains the biomass-derived ethylene glycol.
  • the content of the biomass-derived ethylene glycol in the matte polyester film is not more than 5 wt%.
  • the content of carbon derived from biomass measured by radioactive elements (C 14 ) is not more than 5%.
  • the r-PET bottle flakes contain a metal catalyst, so that the final matte polyester film also contains the metal catalyst.
  • the metal catalyst is at least one selected from the group consisting of antimony (Sb), germanium (Ge), and titanium (Ti). Based on a total weight of 100 wt% of the matte polyester film, the content of the metal catalyst in the matte polyester film is 0.0003 wt% to 0.04 wt%.
  • Step S120 includes: physically regenerating a part of the recycled polyester material to obtain physically regenerated polyester chips.
  • the physically regenerated polyester chips have a first intrinsic viscosity.
  • the first intrinsic viscosity of the physically regenerated polyester chips is generally not less than 0.60 dL/g.
  • the first intrinsic viscosity is 0.65 dL/g to 0.90 dL/g. More preferably, the first intrinsic viscosity is 0.65 dL/g to 0.80 dL/g.
  • the manufacturing steps of the physically regenerated polyester chips include: pulverizing a part of the recycled polyester material (such as r-PET bottle flakes) by a physical mechanical means to reduce the time and energy consumption required to melt the recycled polyester material. Then, the pulverized recycled polyester material is melted, so that the recycled polyester material is in a molten state. Then, a first screen is used to filter the recycled polyester material in the molten state to remove solid impurities in the recycled polyester material. Lastly, the filtered recycled polyester material is extruded and pelletized to form the physically regenerated polyester chips.
  • a part of the recycled polyester material such as r-PET bottle flakes
  • the recycled polyester material is reshaped by cutting, melting, filtering, extruding, and the like in sequence in order to rearrange the polyester molecules in the original recycled polyester material, so as to prepare a plurality of the physically regenerated polyester chips.
  • the polyester molecules of the recycled polyester material are only rearranged but not reorganized, the components (such as metal catalysts, slipping agents, or copolymerized monomers, etc.) originally present in the recycled polyester material are still present in the physically regenerated polyester chips, so that the final matte polyester film also contains these components. Furthermore, the various characteristics of the recycled polyester material itself are also retained in the physically regenerated polyester chips.
  • the recycled polyester material Since the molecular weight of the recycled polyester material in the physical regenerating process is not changed significantly, the recycled polyester material has a relatively high viscosity in a molten state and has worse flow properties. Accordingly, if a screen with an insufficient mesh diameter is used, the issue of poor filter efficiency readily occurs.
  • the mesh diameter of the first screen is preferably between 10 microns and 100 microns.
  • the first screen may screen out solid impurities with a particle size larger than the mesh diameter, but the disclosure is not limited thereto.
  • the physically regenerated polyester chips (physically regenerated polyester resin) obtained by physical regeneration have a higher intrinsic viscosity (not less than 0.60 dL/g). If only the physically regenerated polyester chips (physically regenerated polyester resin) are used, the polyester masterbatch material is only suitable for bottle blowing and spinning processes, not for film extrusion processes.
  • solid-state polymerization To adjust the intrinsic viscosity of the physically regenerated polyester chips may be used solid-state polymerization.
  • the solid-state polymerization method may only be used to increase the intrinsic viscosity of the physically regenerated polyester chips, and may not be used to reduce the intrinsic viscosity of the physically regenerated polyester chips.
  • chemically regenerated polyester chips (chemically regenerated polyester resin) are prepared by a chemical regenerating step in step S130 with a less intrinsic viscosity (not greater than 0.65 dL/g).
  • Step S130 includes: chemically regenerating another part of the recycled polyester to obtain chemically regenerated polyester chips.
  • the chemically regenerated polyester chips have a second intrinsic viscosity, and the second intrinsic viscosity of the chemically regenerated polyester chips is less than the first intrinsic viscosity of the physically regenerated polyester chips.
  • the second intrinsic viscosity of the chemically regenerated polyester chips is generally not more than 0.65 dL/g.
  • the second intrinsic viscosity is 0.40 dL/g to 0.65 dL/g. More preferably, the second intrinsic viscosity is 0.50 dL/g to 0.65 dL/g.
  • the manufacturing steps of the chemically regenerated polyester chips include: cutting or pulverizing another part of the recycled polyester material (such as r-PET bottle flakes) to reduce the time and energy consumption required to depolymerize the recycled polyester material. Then, the cut or pulverized regenerated polyester material is put into a chemical depolymerization solution to depolymerize the regenerated polyester material so as to form a masterbatch material mixture. Next, a second screen is used to filter the masterbatch material mixture to remove solid impurities in the recycled polyester material, thereby reducing the concentration of non-polyester impurities in the masterbatch material mixture.
  • the recycled polyester material such as r-PET bottle flakes
  • the masterbatch material mixture filtered by the second screen is subjected to an esterification reaction, and an inorganic additive or a copolymer monomer is added during the esterification reaction.
  • the monomers and/or oligomers in the masterbatch material mixture are re-polymerized and pelletized to obtain the chemically regenerated polyester chips.
  • the liquid temperature of the chemical depolymerization solution may be, for example, between 160 °C and 250 °C, but the disclosure is not limited thereto.
  • the mesh diameter of the second screen is less than the mesh diameter of the first screen.
  • the chemical depolymerization solution may cause chain scission to the polyester molecules in the recycled polyester material, so as to achieve the effect of depolymerization, and a polyester composition with shorter molecular chain and an ester monomer composed of one diacid unit and two diol units may be further obtained, such as bis(2-hydroxyethyl) terephthalate (BHET). That is, the molecular weight of the masterbatch material mixture is less than the molecular weight of the recycled polyester material.
  • BHET bis(2-hydroxyethyl) terephthalate
  • the chemical depolymerization solution may be, for example, a solution of water, methanol, ethanol, ethylene glycol, diethylene glycol, or a combination thereof, but the disclosure is not limited thereto.
  • water is used for hydrolysis
  • methanol, ethanol, ethylene glycol, or diethylene glycol is used for alcoholysis.
  • the chemical regenerating step involves "depolymerization and repolymerization of polyester molecules in the recycled polyester material" to depolymerize the polyester molecules into molecules with smaller molecular weight and further repolymerize the molecules into a new polyester resin.
  • the method for preparing the chemically regenerated polyester chips is not limited to those described in the above embodiments, and the chemically regenerated polyester chips may also be prepared by hydrolysis or supercritical fluid methods.
  • the hydrolysis method is performed with the recycled polyester material in an alkaline solution, wherein by adjusting a certain temperature and pressure, and under the irradiation of microwave radiation, the polyester molecules are completely decomposed into monomers.
  • the supercritical fluid method is to decompose the recycled polyester material into a small amount of monomers and oligomers in supercritical fluid methanol. In particular, the yield of monomers and oligomers is affected by the reaction temperature and reaction time.
  • the recycled polyester material may be depolymerized into monomers with small molecular weight. Therefore, the impurities (such as colloidal impurities or other non-polyester impurities) originally present in the recycled polyester material (such as r-PET bottle flakes) may be more readily excluded by filtering compared to physical recycling methods.
  • the impurities such as colloidal impurities or other non-polyester impurities
  • the chemical regenerating operation may reduce the molecular weight of the recycled polyester material (such as forming polyester compositions and compound monomers with shorter molecular chains), the recycled polyester material has a less viscosity after being depolymerized, and the flow properties thereof are better. Accordingly, the chemical regenerating operation may adopt a screen with a smaller mesh diameter to eliminate impurities with a smaller particle size in the polyester material.
  • the mesh diameter of the second screen is preferably between 1 micron and 10 microns.
  • the second screen may screen out solid impurities with a particle size larger than the mesh diameter, but the disclosure is not limited thereto.
  • the physical regenerating step may only filter and recycle solid impurities with a larger particle size in the polyester material, and the chemical regenerating step may filter and recycle solid impurities with a smaller particle size in the polyester material. Thereby, the production quality of the matte polyester film may be effectively improved.
  • the chemically regenerated polyester chips produced by the chemical regenerating step generally have a less intrinsic viscosity.
  • the intrinsic viscosity of the chemically regenerated polyester chips is easier to control, and the intrinsic viscosity of the chemically regenerated polyester chips may be adjusted to be less than the intrinsic viscosity of the physically regenerated polyester chips.
  • Step S140 includes: mixing matte regenerated polyester chips, the physically regenerated polyester chips, and the chemically regenerated polyester chips according to a predetermined intrinsic viscosity so as to form a polyester masterbatch material.
  • the intrinsic viscosity of the polyester masterbatch material is suitable for a film-making process.
  • the intrinsic viscosity of the polyester masterbatch material is 0.50 dL/g to 0.8 dL/g.
  • the intrinsic viscosity of the polyester masterbatch material is 0.50 dL/g to 0.60 dL/g.
  • the final matte polyester film has the predetermined intrinsic viscosity, which is 0.50 dL/g to 0.75 dL/g.
  • the predetermined intrinsic viscosity is 0.50 dL/g to 0.60 dL/g.
  • the matte regenerated polyester chips, the physically regenerated polyester chips, and the chemically regenerated polyester chips are mixed with each other in a predetermined weight ratio according to the predetermined intrinsic viscosity. Accordingly, the mixed matte regenerated polyester chips, physically regenerated polyester chips, and chemically regenerated polyester chips may have an intrinsic viscosity suitable for a film-making process.
  • the matte regenerated polyester masterbatch material includes a matte additive, and the matte additive is at least one material selected from the group consisting of silica particles, calcium carbonate particles, alumina particles, and talc particles.
  • the particle size of the matte additive is between 0.1 ⁇ m and 10 ⁇ m.
  • the content of the matte additive is 0.1 weight percent to 20 weight percent.
  • the matte regenerated polyester chips may be prepared by a physical regenerating step or a chemical regenerating step.
  • the matte regenerated polyester chips include at least one of the physically matte regenerated polyester chips and the chemically matte regenerated polyester chips.
  • the method for manufacturing the physically matte regenerated polyester chips includes melting a part of the recycled polyester material to obtain a first molten mixture.
  • a matte additive is added to the first molten mixture to form a second molten mixture.
  • the second molten mixture is reshaped to obtain the physically matte regenerated polyester chips.
  • the first molten mixture may, for example, be filtered through the first screen first, and then the matte additive is added to form the second molten mixture.
  • the physically matte regenerated polyester chips are added with the matte additive, the intrinsic viscosity of the physically matte regenerated polyester chips is reduced.
  • the intrinsic viscosity of the physically matte regenerated polyester chips is between 0.58 dL/g and 0.72 dL/g.
  • the method for manufacturing the chemically matte regenerated polyester chips includes: depolymerizing another part of the recycled polyester material to obtain a first oligomer mixture.
  • a matte additive is added to the first oligomer mixture to form a second oligomer mixture.
  • the second oligomer mixture is repolymerized to obtain the chemically matte regenerated polyester chips.
  • the first oligomer mixture may, for example, be filtered through the second screen first, and then the matte additive is added to form the second oligomer mixture.
  • the chemically matte regenerated polyester chips are added with the matte additive, the intrinsic viscosity thereof is reduced.
  • the intrinsic viscosity of the chemically matte regenerated polyester chips is between 0.45 dL/g and 0.58 dL/g.
  • the various regenerated polyester chips all have a suitable usage range.
  • the amount of the physically regenerated polyester chips is preferably 50 parts by weight to 95 parts by weight, more preferably 60 parts by weight to 80 parts by weight.
  • the amount of the chemically regenerated polyester chips is between 5 parts by weight and 50 parts by weight, preferably between 20 parts by weight and 40 parts by weight, but the disclosure is not limited thereto.
  • the amount of the physically regenerated polyester chips is higher than the amount of the chemically regenerated polyester chips, but the disclosure is not limited thereto.
  • Step S150 includes: melting and then extruding the polyester masterbatch material to form a matte polyester film.
  • the matte polyester film has a predetermined intrinsic viscosity.
  • the physically regenerated polyester chips (including the physically matte regenerated polyester chips) form a physically regenerated polyester resin
  • the chemically regenerated polyester chips (including the chemically matte regenerated polyester chips) form a chemically regenerated polyester resin
  • the matte additive in the matte regenerated polyester chips is evenly dispersed in the physically regenerated polyester resin and the chemically regenerated polyester resin.
  • the content of the physically regenerated polyester resin is preferably 50 wt% to 95 wt%, and more preferably 60 wt% to 80 wt%.
  • the content of the chemically regenerated polyester resin is preferably 5 wt% to 50 wt%, and is more preferably 20 wt% to 40 wt%.
  • the content of the matte additive is 0.1 wt% to 20 wt%.
  • the total content of the physically regenerated polyester resin and the chemically regenerated polyester resin is 55 wt% to 100 wt%, and the total content is more preferably 70 wt% to 100 wt%.
  • the method for manufacturing the matte polyester film of the present embodiment may be performed by using a high proportion of the recycled polyester material without the addition of a virgin polyester resin, or only a small amount of the virgin polyester resin needs to be added.
  • the amount of the virgin polyester resin is usually not more than 50 parts by weight, preferably, the virgin polyester resin is not more than 30 parts by weight, and more preferably, the virgin polyester resin is not more than 10 parts by weight.
  • the physically regenerated polyester chips have a first acid value
  • the chemically regenerated polyester chips have a second acid value
  • the second acid value is greater than the first acid value.
  • the first acid value is between 10 mgKOH/g and 40 mgKOH/g
  • the second acid value is between 20 mgKOH/g and 70 mgKOH/g.
  • the physically regenerated polyester chips have a first molecular weight distribution 1
  • the chemically regenerated polyester chips have a second molecular weight distribution 2
  • the distribution range of the second molecular weight distribution 2 is wider than the distribution range of the first molecular weight distribution 1.
  • the polyester masterbatch material (matte regenerated polyester chips, physically regenerated polyester chips, and chemically regenerated polyester chips) have a third molecular weight distribution 3, and the distribution range of the third molecular weight distribution 3 is between the first molecular weight distribution 1 and the second molecular weight distribution 2.
  • the molecular weight distribution of the chemically regenerated polyester chips is wider, which may contribute to the productivity of the film-making process, but the physical properties (such as: mechanical properties) of a matte polyester film produced only using the chemically regenerated polyester chips are worse. Furthermore, the production cost of the chemically regenerated polyester chips is higher.
  • the molecular weight distribution of the physically regenerated polyester chips is narrower, which is not good for the productivity of the film-making process, but a matte polyester film with stronger mechanical properties may be produced, with better physical properties. In other words, completely using physical recycling or chemical recycling is not ideal.
  • the characteristic of the method for manufacturing a matte polyester film of an embodiment of the disclosure is that the use of the physically regenerated polyester chips and the chemically regenerated polyester chips at the same time may improve the productivity of the film-making process, improve the physical properties of the matte polyester film, and reduce the production cost of the matte polyester film.
  • the above is the method for manufacturing a matte polyester film of an embodiment of the disclosure, and the following describes the matte polyester film of an embodiment of the disclosure.
  • the matte polyester film is formed by the above manufacturing method, but the disclosure is not limited thereto.
  • the material of the matte polyester film includes a physically regenerated polyester resin, a chemically regenerated polyester resin, and a matte additive.
  • the physically regenerated polyester resin is formed from physically regenerated polyester chips, and the physically regenerated polyester chips have a first intrinsic viscosity.
  • the chemically regenerated polyester resin is formed from chemically regenerated polyester chips, the chemically regenerated polyester chips have a second intrinsic viscosity, and the second intrinsic viscosity is less than the first intrinsic viscosity.
  • the matte additive is dispersed between the chemically regenerated polyester resin and the physically regenerated polyester resin.
  • the physically regenerated polyester chips and the chemically regenerated polyester chips are mixed according to a predetermined intrinsic viscosity as the target, so that the resulting matte polyester film may have the predetermined intrinsic viscosity.
  • the first intrinsic viscosity of the physically regenerated polyester chips is not less than 0.60 dL/g
  • the second intrinsic viscosity of the chemically regenerated polyester chips is not more than 0.65 dL/g
  • the predetermined intrinsic viscosity is 0.40 dL/g to 0.75 dL/g.
  • the first intrinsic viscosity of the physically regenerated polyester chips is 0.65 dL/g to 0.80 dL/g
  • the second intrinsic viscosity of the chemically regenerated polyester chips is 0.50 dL/g to 0.65 dL/g
  • the matte polyester film has a predetermined intrinsic viscosity between 0.50 dL/g and 0.60 dL/g.
  • the matte polyester film has an acid value between 10 mgKOH/g and 80 mgKOH/g, and preferably between 40 mgKOH/g and 70 mgKOH/g.
  • the method for measuring the acid value range of the matte polyester film is to use a titration method, which is performed with reference to the ASTM D7409-15 standard test method.
  • the matte polyester film When the acid value of the matte polyester film is between 10 mgKOH/g and 80 mgKOH/g, the matte polyester film has the effects of heat resistance and hydrolysis resistance under the condition of low acid value.
  • the plurality of physically regenerated polyester chips and the plurality of chemically regenerated polyester chips are all obtained by recycling the recycled polyester material and pelletizing the recycled polyester material.
  • the recycled polyester material is r-PET bottle flakes.
  • the matte polyester film meets the following conditions: (i) based on a total weight of 100 mol% of the matte polyester film, the content of isophthalic acid in the matte polyester film is between 0.7 mol% and 4.0 mol%; (ii) based on a total weight of 100 wt% of the matte polyester film, the content of biomass-derived ethylene glycol in the matte polyester film is not more than 5 wt%; (iii) the haze of the matte polyester film is between 15% and 95%; (iv) the visible light transmittance of the matte polyester film is not less than 60%, and preferably not less than 80%; (v) the surface roughness (Ra) of the matte polyester film is between 100 nm and 400 nm (the surface roughness measurement method is based on DIN EN ISO4287/4288); and (vi) the friction coefficient of the matte polyester film is between 0.2 and 0.6.
  • the method for measuring the friction coefficient of the matte polyester film is based on ASTM D1894.
  • the storage modulus of the matte polyester film measured at 150 ⁇ 2 °C and 10 Hz is between 4.2 ⁇ 10 9 dyne/cm 2 and 6.8 ⁇ 10 9 dyne/cm 2 , and preferably between 4.2 ⁇ 10 9 dyne/cm 2 and 6.6 ⁇ 10 9 dyne/cm 2 .
  • the storage modulus of the matte polyester film is the average value of the storage modulus of the matte polyester film in the MD direction and the TD direction measured by a dynamic viscoelasticity measuring apparatus. Please refer to FIG. 3 and FIG. 4 for specific measurement results, but the disclosure is not limited thereto.
  • the polyester masterbatch material may be adjusted to have a predetermined intrinsic viscosity, so as to be suitable for a film extrusion process, and a higher proportion of the recycled polyester masterbatch material is achieved.

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EP21193708.1A 2021-01-29 2021-08-30 Film de polyester mat et son procédé de fabrication Pending EP4036160A3 (fr)

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CN114806093A (zh) 2022-07-29
EP4036160A3 (fr) 2022-08-10
JP7324261B2 (ja) 2023-08-09
TW202229423A (zh) 2022-08-01
JP2022117420A (ja) 2022-08-10
JP2023085412A (ja) 2023-06-20
TWI742994B (zh) 2021-10-11

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